Derivatives of perfluorinated hydrocarbons

ABSTRACT

DERIVATIVES OF PERFLUORINATED HYDROCARBONS HAVING AN ALKENYLCARBOXAMIDO GROUPING IN THE MOLECULE.

United States Patent ABSTRACT OF THE DISCLOSURE Derivatives of perfluorinated hydrocarbons having an alkenylcarboxamido grouping in the molecule.

The invention relates to new derivatives of perfluorinated hydrocarbons which essentially contain an alkenylcarboxamido grouping in the molecule.

The invention also relates to a process for the production of the new substances and their use as oil repellents.

The new compounds have the Formula I:

R R (I) in which R denotes perfluorinated alkyl having from three to eleven carbon atoms;

R R R and R which may be identical or difierent,

denote hydrogen, alkyl, aryl, aralkyl or cycloalkyl;

A denotes a radical of the formula:

B denotes a radical of the formula: NR or (CHR 0 or a single valency; and R denotes hydrogen or a radical of the formula:

where x denotes one of the integers 0 to 4;

y denotes one of the integers 0 to 3;

2 denotes one of the integers 0 to 2;

n denotes one of the integers 0 to 4;

p denotes one of the integers 0 to 4; and q denotes one of the integers 0 and 1;

and when q denotes zero, 2: and p denote zero or 1.

3,806,528 Patented Apr. 23, 1974 ice x preferably denotes 1 to 3, 2 preferably denotes 1 or 2, n preferably denotes zero or 1 and p preferably denotes 1 to 3.

In the context of the invention, lower alkyl, aryl, aralkyl and cycloalkyl which R R R and R in Formula I denote (in addition to hydrogen) include aliphatic radicals having one to six, aromatic radicals having six to ten, araliphatic radicals having seven to twelve or cycloaliphatic radicals having dive to eight carbon atoms. Examples of preferred radicals are methyl, ethyl, propyl, phenyl, benzyl or cyclohexyl radicals.

The perfluorinated alkyl radical R contains three to eleven, preferably five to ten, carbon atoms. When q denotes 1, the alkyl radicals are derived from perfluorinated carboxylic acids whose perfluoroalkyl radical is defined by the abovementioned number of carbon atoms, examples of preferred acids being perfluorocapric, perfluoro caproic and perfluorocaprylic acid because these are the easiest to obtain. When q denotes zero, the alkyl radicals are derived from the amines derived in turn from the abovementioned carboxylic acids, for example by Hoffmann degradation of the corresponding acid amides or by reduction of the corresponding nitriles. In both cases R of the formula: CF -(CF is of special industrial interest.

The usual prior art methods of producing these acids result in contamination by up to 15% of higher fluorinated carboxylic acids having a maximum of twelve carbon atoms.

Examples of individual representatives of the new compounds are the substances having the formulae:

Substances of Formula I are accessible by successively reacting a compound of Formula II:

in which A, B and x have the meanings given for Formula I with a perfluorocarboxylic acid derivative of the formula: R -COU in which R has the meanings given for Formula I and U denotes chlorine or an ester group ing, and with a N-(l-alkenyDcarbamic acid chloride of Formula III:

or (when R denotes hydrogen) the alkenyl isocyanate of Formula IV:

R R (IV) ylformamide and then at 0 to 5 C. the perfluorocarboxylic acid derivative with or without a substance which binds acid, for example an alkali metal hydroxide, an alkali metal carbonate or preferably a tertiary amine such as triethylamine, tripropylamine, ethyldiisopropylamine or pyridine is added. When an acid-binding substance is used, the amounts of the reactants are chosen so that to each mole of compound having Formula II with n OH or NH groups there is available n-l moles of perfluorocarboxylic acid derivative and, when a perfluorocarboxylic acid chloride is used, from 1 to 3 moles of acid-binding substance.

Sometimes it is advantageous however to use the compound having the Formula II itself as the acid-binding substance. The reaction mixture is stirred for from one hour to twenty-four hours at room temperature to complete the reaction. The intermediates formed may be isolated by stirring the reaction mixture with water, if necessary removing the solvent at subatmospheric pressure, suction filtration and drying of the precipitate. The intermediate having Formula V:

thus formed (in which the variables have the meanings given for Formula I) may be reacted under the conditions mentioned above with the carbamyl chloride or isocyanate having Formula III or IV.

N-(l-alkenyD-carbamyl chlorides having Formula III can be prepared in a simple manner by reacting compounds having Formula VI:

R R (VI) in which R R R and R have the meanings given for Formula I with phosgene. The alkenyl isocyanates having Formula IV may then be prepared from the compounds having Formula III (when R denotes hydrogen) by subjecting them to a thermal treatment.

A direct method of obtaining the alkenyl isocyanates however is by Curtius degradation of azides of a,,B-unsaturated carboxylic acids.

The following method has proved to be very suitable for the production of compounds having Formula I: a compound of Formula V is placed in an inert non-polar solvent such as benzene, toluene, methyl chloride, cyclohexane, ligroin, ether or dioxane and preferably ether and the N-(l-alkenyl) isocyanate is slowly added dissolved in a little solvent at from 0 to 5C. The reaction mixture is stirred until reaction is completed for another twelve to fourteen hours at room temperature and the substituted alkenyl-urea or the alkenylurethane formed is suction filtered or the solvent is carefully distilled off at subatmospheric pressure and the end product is isolated in the usual way. When a carbamyl chloride is used as reactant instead of an isocyanate, the advantageous procedure is by reaction of the compounds of Formula III in the presence of an equivalent amount of an acidbinding substance, as for example a tertiary amine, potassium carbonate or sodium carbonate, preferably a tertiary amine, together with the alkenylcarbamyl chloride: The products formed are then washed with water to free them from the hydrochlorides simultaneously formed.

The substituted alkenylureas of Formula I are usually obtained as white crystalline substances and the alkenyl urethanes usually as yellow to brown oils or pastes which are soluble in organic solvents such as acetone, methanol and the like. The substances according to the invention are very suitable as oil repellents for surfaces of all types.

They have special importance for the oil repellent finishing of textile materials or fibers of natural and artificial material such as wool, silk, polyamide fibers, polyester fibers, polyolefin fibers, cellulose ester fibers and particularly fibers of natural and regenerated cellulose and mixtures thereof with synthetic fibers. The substances of Formula I may be applied to the surfaces to be treated in the form of their solutions in organic solvents or in the form of aqueous dispersions of these solutions or in the form of the substances themselves. The solutions or dispersions are then dried at room temperature or preferably at elevated temperature (90 to 150 C.). After the drying of the solutions or dispersions, the surfaces are oil-repellent.

The finishing effects are particularly resistant to washing in the treatment of textile materials when the textiles which have been impregnated with the substances of Formula I are heated for about three to seven, preferably about five, minutes at 80 to 150 C. after they have been dried. The effects are very pronounced especially on material consisting of or containing cellulose and reach the optimum at an application of 0.1 to 1.5%, preferably 0.5 to 1.0%, by weight of the substance according to the invention, based on the dry textile material.

The resistance of the finish, particularly to the action of water and to washing, can be considerably improved when there are applied to the surfaces to be treated not only the substances having the Formula I but also heatcurable resin-forming substances and if necessary catalysts which support the thermal curing of these resinforming substances, followed by the heat curing. Examples of heat-curable resin forming substances are those known as aminoplast forming substances, i.e. low molecular weight substances containing N-methylol and/or N- alkoxymethyl groups. Examples of such substances are polymethylol compounds (which may if desired be partly or wholly etherified) of urea, monoalkylureas, symmetrical dialkylureas, cyclic ureas such as N,N'-ethylenurea (=imidazolidone-2),

N,N'-1,2-propyleneurea (-=4-methylimidazolidone-2),

N,N'-1,3-propyleneurea (=N,N'-trimethyleneurea or hexahydropyrimidone-Z),

S-hydroxyhexahydropyrimidone-Z,

4-hydroxy-5,5-dialkylhexahydropyrimidone,

4-alkoxy-5,5-dialkylhexahydropyrimidone,

hexahydro-1,3,5-triazinone-2- and its S-alkyl and S-hydroxyalkyl derivatives,

glyoxal monoureine (4,5-dihydroxyimidazolidone-2) and urones,

monocarbamic and dicarbamic esters such as ethyl carbamate,

propyl carbamate,

butyl carbamate,

,B-hydroxyethyl carbamate,

,B-methoxyethyl carbamate,

octyl carbamate,

ethyl N-methylcarbamate, and

butyl N-ethylcarbamate and dicarbamic esters and di-N-ethylcarbamic esters of ethylene glycol,

1,3-butanediol,

1,4-butanediol and 1,6-hexanediol,

of aminotriazines such as melamine, ammeline and ammelide, of guanidine, dicyanodia'mide, dicyanodiamidine, thiourea and acetylenediurea ('=glyoxal diureine).

The catalysts for assisting the heat curing of aminoplast-forming substances include particularly acid and potentially acid catalysts, i.e. strong or medium strength acids, i.e. acids having a dissociation constant K or K of more than such as hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, glycolic acid, maleic acid, monochloroacetic acid, trichloroacetic acid, tartaric acid and citric acid, or substances such as esters 01' particularly salts, which themselves have little or no acidity but which liberate by hydrolysis or thermal influences such an amount of acid that the cure of the aminoplastforming substances is accelerated. In this context, cure includes not only the reaction of the molecules of the aminoplast-forming substances with one another but also their reaction with reactive groups of the surface to be finished. Salts which are suitable as potentially acid catalysts include for example those of ammonia, amines or polyvalent metals and medium strength or preferably strong acids, for example ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium nitrate, dimonoethanolammonium hydrogen phosphate, ethanolammonium chloride, 1-hydroxy-2-methylpropylammonium- 2-chloride, magnesium chloride, aluminum chloride, zinc chloride, zinc nitrate, zinc fluoroborate and zirconyl chloride. Mixtures of two or more of these catalysts may also be used.

Curing of the resin-forming substances may for example be carried out by conventional methods by heating the articles bearing on their surfaces the resin-forming substances, the substances of Formula I and the catalysts, for from five to fifteen minutes at a temperature of more than C., preferably at to C.

It has also proved to be very suitable to apply an ad ditional oil-repellent, in addition to the substance of Formula I, with or without the resin-forming substance and the catalyst, to the surface to be made oil-repellent. Examples of oil-repellents are parafiin emulsions, stearylurea and condensation products of the same with formaldehyde with or without other aminoplast-forming substances, stearic hydrazide and N-stearoyl-N',N-ethylenurea.

Textiles finished in this way are strongly oil-repellent and the oil repellency is accompanied by water repellency and soil repellency.

The substances of Formula I may be applied from an organic phase or from an aqueous phase. In the latter case, the substance according to the invention has to be present in a form appropriately emulsified or dispersed in the aqueous phase.

Two baths are used when the substance of Formula I is applied from an organic phase and it is desired at the same time to achieve a creaseproof finish and oil repellency.

1st bath.-Oil-repellent agent according to the invention (organic phase);

2nd bath.Heat-curable (aqueous phase).

When the substances of Formula I are in the form of aqueous emulsions, it is convenient to use a method having one bath with the creaseproofing agent.

Not only textiles, but also other materials such as wood, paper, leather and plastics may be given an oil-repellent impregnation or coating with the compounds of the invention.

,The following examples illustrate the invention. The parts specified are by weight.

'EXAMPLES 1 TO 14 resin-forming substance I.-Production of the perfluorinated hydrocarbons 0.1 mole of the perfluoro compound of Formula V is dissolved in 600 to 800 parts of dry ether and while stirring 0.1 mole of vinyl isocyanate per free reactive -NH or -OH group, dissolved in 80 to 100 parts of absolute ether, is added at a temperature of 0 to 5 C. in the course of 20 to 30 minutes. To complete the reaction, the whole is stirred first for another hour at 0 C. and then for another twelve to fifteen hours at room temperature. The solvent is then removed under mild conditions at subatmospheric pressure and the viscous residue is dried for a short time or the crystalline product suction filtered and washed with a little dry ether.

In the table:

E=Example No. SP=Starting product EB=End product Y=Yield in percent mp=Melting point in C. AR=Analytical results C H N =C H N calculated Cf Hg N1=C H N found.

II.-Making textile material oil-repellent:

10 parts of any of the products of Formula I obtained as described above is dissolved in 1000 parts of acetone. Cotton poplin is padded at room temperature with the solution so that the liquor take-up is 80%. Thus 0.8% of substance remains on the textile material after it has been dried at 80 C. and condensed for five minutes at 150 C. The cloth finished in this way has good oil repellency. A mixture of 10 parts of mineral oil having a viscosity of 78 to 84 centistokes (at 50 C.) and 90 parts of n-heptane is prevented from spreading.

We claim:

1. A compound of the formula wherein R is perfluorinated alkyl of 3 to 11 carbon atoms;

'R R R and R each is hydrogen, lower alkyl, phenyl,

benzyl or cycloalkyl of 5 to 8 carbon atoms;

as is an integer of 1 to 3;

n is an integer of to 1; and

p is an integer of l to 3.

2. A compound as claimed in claim 1 wherein R R R and R each is hydrogen, methyl, ethyl, propyl, phenyl, benzyl or cyclohexyl.

3. A compound as claimed in claim 1 wherein R R R and R each is hydrogen or methyl.

References Cited UNITED STATES PATENTS ELBERT L. ROBERTS, Primary Examiner E. G. LOVE, Assistant Examiner US. Cl. X.R.

8115.6, 116.2, 127.5, 128 R; 117-121, 138.8 B, 138.8 F, 138.8 N, 141, 144; 260-70, 243 B, 268 C, 268 R,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,806,528 DATED April 23, 1974 \NVENTOR(S) 1 Heinz Eilingsfeld et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Column 1, after Line 8, insert "Claims priority, application Germany, September 9, 1970, P 20 44 656.4"

Signed and Scaled this twenty-second D3) Of June 1976 [SEAL] Arrest:

RUTH c. MASON a c. MARSHALL mum Arresting Officer Commissioner of Patents and Trademarks 

